EP0166416B1 - Procédé de polymérisation de monomères de chlorure de vinyle en suspension aqueux - Google Patents

Procédé de polymérisation de monomères de chlorure de vinyle en suspension aqueux Download PDF

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Publication number
EP0166416B1
EP0166416B1 EP85107822A EP85107822A EP0166416B1 EP 0166416 B1 EP0166416 B1 EP 0166416B1 EP 85107822 A EP85107822 A EP 85107822A EP 85107822 A EP85107822 A EP 85107822A EP 0166416 B1 EP0166416 B1 EP 0166416B1
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EP
European Patent Office
Prior art keywords
vinyl chloride
weight
monomer
aqueous medium
polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85107822A
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German (de)
English (en)
Other versions
EP0166416A2 (fr
EP0166416A3 (en
Inventor
Kenichi Itoh
Genji Noguki
Motoaki Tanaka
Hitoshi Ohba
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
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Publication date
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Priority to CN85105492.7A priority Critical patent/CN1005717B/zh
Publication of EP0166416A2 publication Critical patent/EP0166416A2/fr
Publication of EP0166416A3 publication Critical patent/EP0166416A3/en
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Publication of EP0166416B1 publication Critical patent/EP0166416B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04C—ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT PUMPS
    • F04C29/00—Component parts, details or accessories of pumps or pumping installations, not provided for in groups F04C18/00 - F04C28/00
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04C—ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT PUMPS
    • F04C23/00—Combinations of two or more pumps, each being of rotary-piston or oscillating-piston type, specially adapted for elastic fluids; Pumping installations specially adapted for elastic fluids; Multi-stage pumps specially adapted for elastic fluids
    • F04C23/008—Hermetic pumps
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04C—ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT PUMPS
    • F04C2240/00—Components
    • F04C2240/60—Shafts
    • F04C2240/603—Shafts with internal channels for fluid distribution, e.g. hollow shaft
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S417/00—Pumps
    • Y10S417/902—Hermetically sealed motor pump unit
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49229—Prime mover or fluid pump making
    • Y10T29/49236—Fluid pump or compressor making
    • Y10T29/4924—Scroll or peristaltic type

Definitions

  • the present invention relates to an improved method for the polymerization of vinyl chloride monomer in an aqueous medium or, more particularly, to a method for the polymerization of vinyl chloride in an aqueous medium, which method is outstandingly freed from the problem of the polymer scale deposition on the inner walls of the polymerization reactor and surfaces of stirrer and other parts coming into contact with the monomer during the polymerization reaction.
  • the most widely undertaken method for the polymerization of vinyl chloride or a monomer mixture mainly composed of vinyl chloride is the suspension polymerization of the monomer or monomer mixture in an aqueous medium in the presence of a monomer-soluble polymerization initiator.
  • a monomer-soluble polymerization initiator As is well known, one of the serious problems in the suspension polymerization of vinyl chloride or the like monomer is the deposition of polymer scale on the inner walls of the polymerization reactor and surfaces of the stirrer and other parts coming into contact with the monomer during the polymerization reaction.
  • the cooling capacity of the polymerization reactor is greatly decreased resulting in the decrease in the productivity and the polymer scale coming off the reactor walls is eventually intermixed with the polymer product to cause degradation of the product quality.
  • the polymer scale deposited on the surfaces must be removed to prepare for the next run of the polymerization taking a great deal of labor and time while such a cleaning work of the reactor involves a very serious problem of the workers' health due to the toxicity of the vinyl chloride monomer absorbed in the polymer scale in a considerably large amount.
  • One of the approaches for preventing polymer scale deposition in the suspension polymerization of vinyl chloride is to provide the reactor walls with a coating of certain compounds insusceptible to the deposition of the polymer scale.
  • Various types of coating materials have been proposed hitherto including polar organic compounds such as amines, quinones, aldehydes and the like, dyes and pigments, reaction products of a polar organic compound or dye with a metal salt, mixtures of an electron donor compound and an electron acceptor compound, inorganic salts or complex compounds, and others.
  • Japanese Patent Kohyo 57-5000614 and 57-500650 teach admixture of the aqueous medium for the suspension polymerization of vinyl chloride with a dispersing agent which is a water-insoluble crosslinked polymer prepared by the crosslinking copolymerization of acrylic acid and a crosslinkable monomer such as allyl pentaerithritol and allyl saccharose. This method, however, is not quite satisfactory in respect of the rather low effectiveness of the method for the prevention of polymer scale deposition.
  • WO-A-81/03334 describes a process for suspension polymerization of vinyl chloride and optionally co-monomers in the presence of a non-ionic surface active agent, a monomer-soluble initiator and a cross-linked co-polymer having carboxyl groups.
  • This known cross-linked copolymer is derived from cross-linking monomer units which are mainly allyl pentaerythritol and allyl sucrose.
  • Another object of the invention is to provide an improvement in the suspension polymerization of vinyl chloride, according to which the amount of polymer scale deposition on the reactor walls can be greatly decreased by the admixture of the aqueous polymerization medium with a specific additive compound.
  • the above mentioned polymerizable unsaturated carboxylic acid is typically acrylic acid and the crosslinking agent represented by the general formula (I) is typically bisallyl or bismethallyl ether of diethyleneglycol.
  • the improvement provided by the invention comprises admixture of a specific crosslinked water-soluble copolymer and a non-ionic surface active agent in combination.
  • the copolymer is obtained by the copolymerization of a polymerizable unsaturated carboxylic acid compound and a crosslinking agent represented by the general formula (I) in which each symbol has the meaning as defined above.
  • Each of the suffixes p, q and r is zero or a positive integer by definition although it can be a number with a fraction as an average value.
  • Exemplary of the polymerizable unsaturated carboxylic acid compound are: acrylic acid; methacrylic acid; itaconic acid; chloroacrylic acid; cyanoacrylic acid; a-phenylacrylic acid; a-benzylacrylic acid; crotonic acid; maleic acid; fumaric acid; and sorbic acid.
  • These polymerizable carboxylic acids can be used either singly or as a combination of two kinds or more according to need.
  • the crosslinking agent of the general formula (I) is copolymerized with the unsaturated carboxylic acid in an amount from 0.05 to 10 parts byh weight or, preferably, from 0.5 to 5 parts by weight per 100 parts by weight of the unsaturated carboxylic acid.
  • amount of the crosslinking agent is smaller than above, the degree of crosslinking in the resultant copolymer is too small so that the desired effect of preventing polymer scale deposition may be insufficient while a copolymer prepared with a too large amount of the crosslinking agent is no longer soluble in water due to the excessive degree of crosslinking so that such a copolymer is not suitable for use in the inventive method.
  • non-ionic surface active agent suitable for the inventive method are: polyoxyethylene alkyl ethers; polyoxyethylene alkyl phenyl ethers; polyoxyethylene polystyryl phenyl ethers; polyoxyethylene polyoxypropylene block copolymers; partial esters of glycerin with a fatty acid; partial esters of sorbitan with a fatty acid; partial esters of pentaerithritol with a fatty acid; monoesters of propyleneglycol with a fatty acid; partial esters of saccharose with a fatty acid; partial esters of polyoxyethylene sorbitan with a fatty acid; partial esters of polyoxyethylene sorbitol with a fatty acid; partial esters of polyoxyethylene glycerin with a fatty acid; fatty acid est
  • the amounts of the ingredients (a) and (b) added to the aqueous polymerization medium should be in the range from 0.01 to 2 parts by weight or, preferably, from 0.02 to 0.5 part by weight for the ingredient (a) and from 0.005 to 1 part by weight or, preferably, from 0.01 to 0.5 part by weight for the ingredient (b) each per 100 parts by weight of the vinyl chloride monomer or the monomer mixture dispersed in the aqueous medium. These amounts are critical in order that the monomer is dispersed in the aqueous medium in the form of very fine droplets having great stability to cause little deposition of the polymer scale during the polymerization reaction.
  • Suitable coating compositions include those disclosed in Japanese Patent Publications 45-30343, 45-30835, 56-5442, 56-5443 and 56-5444.
  • Particularly preferable as the coating material are polar organic compounds such as dyes, e.g.
  • the polymerization reaction according to the invention is carried out in the presence of a monomer-soluble polymerization initiator.
  • the type of the monomer-soluble polymerization initiator is not particularly limitative and exemplary of the initiators usable in the inventive method are organic peroxides such as diisopropyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, acetyl cyclohexyl sulfonyl peroxide, tert-butyl peroxy pivalate, benzoyl peroxide and lauroyl peroxide and azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethyl valeronitrile, and azobis-4-methoxy-2,4-dimethyl valeronitrile.
  • the method of the present invention is applicable not only to the homopolymerization of vinyl chloride but also to the copolymerization of vinyl chloride with one or more of other copolymerizable monomers known in the art.
  • comonomers include vinyl esters, e.g. vinyl acetate, vinyl ethers, acrylic and methacrylic acids and esters thereof, maleic and fumaric acids and esters thereof, maleic anhydride, aromatic vinyl compounds, e.g. styrene, unsaturated nitrile compounds, e.g. acrylonitrile, vinylidene halides, e.g. vinylidene fluoride and vinylidene chloride, and olefins, e.g. ethylene and propylene.
  • vinyl esters e.g. vinyl acetate, vinyl ethers, acrylic and methacrylic acids and esters thereof, maleic and fumaric acids and esters thereof, maleic anhydride
  • aromatic vinyl compounds e.g.
  • a further enhanced effect of polymer scale prevention can be obtained by admixing the aqueous medium with a small amount, e.g. 1% by weight or smaller, of a water-soluble basic or alkaline compound.
  • the polymerization reaction of the inventive method can be performed under rather conventional polymerization conditions including the amount of the polymerization initiator, temperature and length of time of the polymerization reaction.
  • the inner walls of the same polymerization reactor as used in the preceding examples and the surface of the stirrer were coated with the coating material as indicated in Table 2 below in a coating amount of 0.001 g/m 2 as dried.
  • the reaction was terminated when the pressure inside the reactor had dropped to 59 N/cm 2 (6.0 kg/cm 2 ) after about 6 hours from the start of the reaction and the unreacted vinyl chloride monomer was recovered followed by discharging of the polymerization slurry to visually examine the condition of the reactor walls.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Claims (6)

1. Procédé pour la polymérisation en suspension du monomère chlorure de vinyle ou d'un mélange de monomères essentiellement constitué de chlorure de vinyle, en milieu aqueux, en présence d'un amorceur de polymérisation soluble dans le monomère, qui comprend l'introduction dans le milieu aqueux de:
(a) un copolymère réticulé hydrosoluble d'un composé acide carboxylique insaturé polymérisable et d'un agent réticulant, et
(b) un agent tensioactif non ionique, ledit procédé étant caractérisé en ce que l'agent réticulant est représenté par la formule générale (I):
Figure imgb0006
dans laquelle Me représente un groupe méthyle, Et représente un groupe éthyle, R est un atome d'hydrogene ou un groupe méthyle et p, q et r valent chacun zéro ou un nombre entier positif, étant endendu que p + q + r est un nombre entier positif ne dépassant pas 500, à l'exception du diallyl-éthylène- glycol-éther.
2. Procédé selon la revendication 1, caractérisé en ce que le copolymère réticulé hydrosoluble est un copolymère constitué de 100 parties en poids de l'acide carboxylique insaturé et de 0,05 à 10 parties en poids de l'agent de réticulation.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'acide carboxylique est l'acide acrylique et l'agent réticulant est le bisallyl ou bisméthallyl éther du diéthylène-glycol.
4. Procédé selon la revendication 1, caractérisé en ce que la proportion de composant (a) ajouté au milieu aqueux est dans la gamme de 0,01 à 2 parties en poids pour 100 parties en poids du monomère chlorure de vinyle ou du mélange de monomères.
5. Procédé selon la revendication 1, caractérisé en ce que la proportion de composant (b) ajouté au milieu aqueux est dans la gamme de 0,005 à 1 partie en poids pour 100 parties en poids du monomère chlorure de vinyle ou du mélange de monomères.
6. Procédé selon la revendication 1, caractérisé en ce qu'il comprend en outre le revêtement des parois intérieures du réacteur de polymérisation avec un colorant organique ou un composé organique polaire.
EP85107822A 1984-06-29 1985-06-24 Procédé de polymérisation de monomères de chlorure de vinyle en suspension aqueux Expired EP0166416B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN85105492.7A CN1005717B (zh) 1985-06-24 1985-07-18 氯乙烯单体在水介质中的聚合方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP134177/84 1984-06-29
JP59134177A JPS6114205A (ja) 1984-06-29 1984-06-29 塩化ビニル系単量体の重合方法

Publications (3)

Publication Number Publication Date
EP0166416A2 EP0166416A2 (fr) 1986-01-02
EP0166416A3 EP0166416A3 (en) 1987-01-28
EP0166416B1 true EP0166416B1 (fr) 1989-09-13

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ID=15122241

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EP85107822A Expired EP0166416B1 (fr) 1984-06-29 1985-06-24 Procédé de polymérisation de monomères de chlorure de vinyle en suspension aqueux

Country Status (22)

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US (2) US4694053A (fr)
EP (1) EP0166416B1 (fr)
JP (1) JPS6114205A (fr)
KR (1) KR890002930B1 (fr)
BG (1) BG46307A3 (fr)
BR (1) BR8503113A (fr)
CA (1) CA1261542A (fr)
CS (1) CS266570B2 (fr)
DD (1) DD240021A5 (fr)
DE (1) DE3572986D1 (fr)
EG (1) EG16438A (fr)
ES (1) ES8700275A1 (fr)
HK (1) HK71290A (fr)
HU (1) HUT39754A (fr)
MX (1) MX163233B (fr)
NO (1) NO164602C (fr)
NZ (1) NZ212605A (fr)
PL (1) PL147170B1 (fr)
PT (1) PT80733B (fr)
RO (1) RO91617A (fr)
YU (1) YU45727B (fr)
ZA (1) ZA854866B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6191205A (ja) * 1984-10-12 1986-05-09 Shin Etsu Chem Co Ltd 塩化ビニル系重合体の製造方法
US4742085A (en) * 1987-04-14 1988-05-03 The B. F. Goodrich Company Crosslinked porous skinless particles of PVC resin and process for producing same
EP0518111B1 (fr) * 1991-05-29 1997-04-09 Matsushita Electric Industrial Co., Ltd. Système de projection d'images

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2772258A (en) * 1953-08-13 1956-11-27 Monsanto Chemicals Process for polymerizing vinyl chloride
US2886552A (en) * 1954-06-10 1959-05-12 Diamond Alkali Co Polymerization employing polyvinyl alkyl ethers as suspension stabilizers
GB1150488A (en) * 1966-05-30 1969-04-30 Shinetsu Chem Ind Co Process for the Suspension Polymerisation of Vinyl Chloride
US3907730A (en) * 1973-09-27 1975-09-23 Goodrich Co B F Resinous initiator suspension for olefinic polymerization reactions
JPS5427872B2 (fr) * 1974-03-09 1979-09-12
JPS5253991A (en) * 1975-10-28 1977-04-30 Nissan Chem Ind Ltd Suspension polymerization of vinyl chloride
US4229547A (en) * 1979-03-19 1980-10-21 The B. F. Goodrich Company Method of preparing spherical porous bead-type polymers
DE2911333A1 (de) * 1979-03-22 1980-10-02 Wacker Chemie Gmbh Verfahren zur polymerisation von vinylchlorid nach dem mikrosuspensionsverfahren
EP0052632B1 (fr) * 1980-05-19 1986-04-09 The B.F. GOODRICH Company Procede permettant de preparer des particules de resine vinylique spheriques et poreuses
US4360651A (en) * 1980-05-19 1982-11-23 The B. F. Goodrich Company Process for preparing spherical and porous vinyl resin particles
US4435524A (en) * 1981-09-08 1984-03-06 The B. F. Goodrich Company Process for preparing spherical and porous vinyl resin particles
US4458057A (en) * 1982-10-27 1984-07-03 The Bf Goodrich Company Process for producing spherical and porous vinyl resin particles
JPS59134176A (ja) * 1983-01-19 1984-08-01 住友電気工業株式会社 液体タンク

Also Published As

Publication number Publication date
ES8700275A1 (es) 1986-10-16
MX163233B (es) 1992-03-20
CS472785A2 (en) 1988-09-16
JPH0417202B2 (fr) 1992-03-25
PL254241A1 (en) 1986-06-17
CA1261542A (fr) 1989-09-26
YU107585A (en) 1987-06-30
NZ212605A (en) 1987-11-27
YU45727B (sh) 1992-07-20
USRE33284E (en) 1990-07-31
BG46307A3 (en) 1989-11-15
CS266570B2 (en) 1990-01-12
ES544634A0 (es) 1986-10-16
PL147170B1 (en) 1989-04-29
BR8503113A (pt) 1986-03-18
HK71290A (en) 1990-09-21
PT80733A (en) 1985-12-06
KR860000319A (fr) 1986-01-28
NO164602C (no) 1990-10-24
JPS6114205A (ja) 1986-01-22
ZA854866B (en) 1986-02-26
EP0166416A2 (fr) 1986-01-02
RO91617A (fr) 1987-09-30
DD240021A5 (de) 1986-10-15
EP0166416A3 (en) 1987-01-28
HUT39754A (en) 1986-10-29
KR890002930B1 (ko) 1989-08-12
NO852582L (no) 1985-12-30
NO164602B (no) 1990-07-16
US4694053A (en) 1987-09-15
EG16438A (en) 1989-06-30
DE3572986D1 (en) 1989-10-19
PT80733B (pt) 1987-08-19

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